Method for producing contact lenses from grafted silicon copolymers
专利摘要:
The invention relates to the preparation of graft copolymers from silicones. The method comprises subjecting an article such as a contact lens previously moulded from silicone resins to an UV irradiation step with radiations of wave-length from 1800 to 4000 angströms, in the presence of oxygen, and in a subsequent step contacting said article with an unsaturated monomer compound at a temperature sufficient to ensure the grafting of said compound on the silicone resin. 公开号:SU973027A3 申请号:SU782599202 申请日:1978-03-31 公开日:1982-11-07 发明作者:Важ Жорж 申请人:Эссилор Энтернасьональ Компани Женераль Дъоптик (Фирма); IPC主号:
专利说明:
The invention relates to chemical technology, in particular to a method for preparing contact lenses from grafted silicone copolymers. A method is known for preparing contact lenses from grafted silicone copolymers by molding organosiloxane obtained by reacting in the presence of a platinum catalyst 78 wt.h, dimethylpolysiloxane with a viscosity of 2000 cP, 25 wt.h. siloxane containing units (CH3) g510o (CH) (CH 2) SiO 2. and SiOj. at a ratio of 2.5: 0.4: 3.5 and 5.5 mach. links (CH5) HSiOi and at a ratio of 2: 1, irradiation of the molded substrate with radiation of a wavelength to A in an oxidizing medium and co-imimerization with an unsaturated monomer is N-vinylpyrrolidone at 100-130 ° С Cl. The disadvantage of this method is that the irradiation is carried out with ionizing irradiation with a wavelength of up to 1500 A, so it must be performed in special protective installations in order not to irradiate the operators, as a result. processed products must be transported several times. During these shipments, the surface of the products may be destroyed and contaminated with dust, and during graft copolymerization defects appear that degrade the optical properties of the lenses. The purpose of the invention is to improve fO operational properties of lenses. The goal is achieved by the fact that according to the method of obtaining lenses by molding the organosiloxane obtained by interaction in ts presence of a platinum catalyst 78 Ma.ch. dimethylpolysiloxane with a viscosity of 2000 spP, 25 ma.h. siloxane containing (CH) (CHj) () SiOj and SiOa units at a ratio of 2.5: 0.4: 3.5 and 5.5 wt.h. links. (CH) llSiQ and SiO at a ratio of 2: 1, irradiating the formed substrate in an oxidizing environment and copolymerizing it with an unsaturated monomer at 100-130 s, irradiation is carried out with ultraviolet radiation with a wavelength of 1849-2537 K, and N is used as the unsaturated monomer -vinylpyrrolidone or acrylate ethylpyrrolidone and copolymerization is carried out to a gain of 4.6-11.2%. Example 1 A silicone composition is added to the molds in the form of contact lenses, comprising 78 g of dimethylpolysiloxane blocked at each end by a link of the formula (CH) / j (СН ) 31 OOD and zkos s 2000 cps at 25 g copolymer consisting of units of formulas (Sneh,), (CHg) () SiO and SiO in a ratio of 2.5: 0.4: 3.5; 5.5 g of a polymer consisting of formula units; (CH,) 2 H81 O5 and SiO in a 2: 1 ratio, and 0.001 g of platinum as a solution in octyl alcohol. Forms are kept closed under pressure at 120 ° C. After 3 hours at this temperature, the silokon resin is polymerized and the lenses are removed from the mold. The lenses are then irradiated with rays from a quartz mercury lamp in the open air. A Philips 024 mercury lampr with a power of 4 W and a wavelength of 1849 - 2537 A is used. Each lens is irradiated for 15 minutes from the convex surface and then for 15 minutes from the concave surface 3 cm from the lamp. The lenses are then immersed in a reactor containing N-vinyl pyrrolidone purified by distillation. Continuously sparging with purified nitrogen removes dissolved oxygen from the liquid. The reactor with the contents heated to 130 ° C for 30 minutes Lin from the reactor and rinse with water to remove unvolume pyrrolidone. The degree of graft copolymerization obtained is Side irradiation time, min 4.15 wt.% Polyvinylpyrrolidone relative to the initial lens weight. In another experiment, the graft copolymerization reaction lasts 1 hour at. The degree of graft copolymerization obtained is 4.6% by weight of the initial weight of the lens. Example 2. Silicone molded resin lenses prepared according to the procedure of Example 1 were irradiated with the rays of the same lamp, changing the conditions. After the reaction of graft-copolymerization of N-vinylpyrrolidone, carried out for 30 minutes at, the following is obtained: a) upon irradiation at a distance of 3 cm for 30 minutes on each side, the degree of graft-copolymerization is 5.3%; b) when irradiated at a distance of 1.5 cm for 15 minutes on each side, the degree of graft copolymerization is 6.05% (in weight of the initial weight of the lens). Example 3. A low-pressure Philips TUV 15-watt mercury lamp with a quartz sheath, emitting waves up to 2537 A, is used as a source of ultraviolet rays. The lenses, obtained as in Example 1, are treated in the same way, changing the time of exposure and the duration of contact with the graft monomer. The degrees of graft copolymerization, expressed in the amount of polyvinylpyrrolidone relative to the initial weight of the silicone resin from which the lenses are made, are listed in the table. Example 4. Samples molded in the form of contact lenses according to the method of example 1 from the same silicone resin are placed vertically in quart cell supports and irradiated from both sides with the help of two NRK 125 lamps located respectively on one and the other side at a distance 4 cm from samples. The power of such a lamp in diapapolivinylpyrrolone, weight,% An irradiation zone of up to 2537 A is 9 watts. The irradiation dose at 2537 A obtained by each of the sides under these conditions is 500 W (mW) / cm or 0.13 cal / s per 1 cm.
权利要求:
Claims (1) [1] After irradiation time from 10 s to 10 min according to the samples, they are in contact with N-vinylpyrrolidone under bubbling with nitrogen at 5 3 for 30 min. The degree of graft copolymerization is 11.2% of the weight of the polyvinyl pyrrh lidone based on the total weight of the sample during the irradiation period of 5 minutes. During the irradiation period of 1 min and the duration of contact of the resin with the monomer for 30 min at 100 ° C, the degree of graft copolymerization is 3 wt.%. An increase in the irradiation time of more than 10 minutes does not increase the degree or yield of graft copolymerization. However, decomposition of the polymers is not observed even during the irradiation period of about 1 hour. Example 5. Samples in the form of contact lenses were prepared as described in Example 1, however, 10 to 250 (preferably 100) ppm of hydrochloric acid was added to the polymer mixture before molding. Samples were irradiated with an NRK lamp for 5 minutes as in Example 4, then they were contacted with vinylpyrrolidone for 30 minutes at. The degree of graft copolymerization is 6% by weight. Example 6. Do the same as in example 4, replacing vinylpyrrolidone with ethylpyrrolidone acrylate. During the ultraviolet irradiation time for 5 minutes with a duration of contact with the monomer of 30 minutes at 100 ° C, the degree of graft copolymerization obtained is 8% by weight. Thus, according to the invention, when the substrate is irradiated, non-ionizing radiation is used, which makes it possible to carry out the grafting process under normal conditions without using special protective equipment and, therefore, leads to an improvement in the performance properties of the graft copolymer, since mechanical damage and contamination by dust are eliminated. transportation. The invention The method of obtaining contact lenses from grafted silicone copolymers by molding organosiloxane obtained by reacting in the presence of a platinum catalyst 78 wt.h. dimethylpolysiloxane with a viscosity of 2000 cPs, 25 min.h, a siloxane containing links (clearly,) (with%) (ca2.) sio.2 and a ratio of 2, 5: o, 4: 3, 5 and 5.5 May. h (CH2) H31O2 and SiO units at a ratio of 2: 1, irradiating the formed substrate in an oxidizing medium and copolymerizing it with an unsaturated monomer at 100-130 ° C, characterized in that, to improve the performance properties of the lenses, irradiation is carried out with ultraviolet radiation at a wavelength of 1849 -2537, and N-vinylpyrrolidone or acrylate ethylpyrrolidone is used as the unsaturated monomer and copolymerization is carried out to a gain of 4.6-11.2%. Sources of information taken into account during the examination 1. USSR PIChENT for application No. 2051194/05, cl. C 08 F 283/12, 1974.
类似技术:
公开号 | 公开日 | 专利标题 SU973027A3|1982-11-07|Method for producing contact lenses from grafted silicon copolymers EP1153964B1|2006-07-12|Surface-treated optical article of plastics material and method of surface treatment US3959102A|1976-05-25|Method for preparing a crosslinked graft copolymer of silicone and polyvinylpyrrolidone for use as a contact lens, and a contact lens produced thereby US5805264A|1998-09-08|Process for graft polymerization on surfaces of preformed substates to modify surface properties US5397848A|1995-03-14|Enhancing the hydrophilicity of silicone polymers JP2551580B2|1996-11-06|How to make contact lenses hydrophilic WO1995017689A1|1995-06-29|Method for increasing hydrophilicity of contact lenses US3700573A|1972-10-24|Method of preparation of hydrophilic silicones by radiochemical grafting EP0574352A1|1993-12-15|Process for graft polymerization on surfaces of preformed substrates to modify surface properties US4965026A|1990-10-23|Process for hydroxylating hydrophobic polymer surfaces US5529727A|1996-06-25|Method of treating contact lenses US5017406A|1991-05-21|UV curable compositions cured with polysilane and peroxide initiators US4062627A|1977-12-13|Flexible contact lens JP2002113089A|2002-04-16|Polymer and lens for oculus using it SU614752A3|1978-07-05|Method of manufacturing contact concavo-convex lens Charlesby et al.1962|Crosslinking of polyethylene and paraffins by ultra-violet radiation in the presence of sensitizers US3565779A|1971-02-23|Irradiation cross linked copolymers of n-substituted amides of unsaturated carboxylic acids containing aceto or benzophenone groups Bucio et al.1996|Radiation-grafting of 2-bromoethylacrylate onto polyethylene film by preirradiation method Kang et al.2021|Visible light-degradable supramolecular gels comprising cross-linked polyrotaxanes capped with trithiocarbonate groups EP0302664A2|1989-02-08|Photo polymers and uses thereof RU2058328C1|1996-04-20|Method of producing polymeric material for soft contact lens FR2576601A1|1986-08-01|TERPOLYMERS HAVING THE CHARACTER OF HYDROGELS RU2187515C2|2002-08-20|Method of preparing polymer material for flexible contact lens RU2119927C1|1998-10-10|Method of preparing polymer material for flexible contact lenses US2893937A|1959-07-07|Method of making polymers
同族专利:
公开号 | 公开日 CH630103A5|1982-05-28| JPS53121874A|1978-10-24| ES468279A1|1978-11-16| FR2385763A1|1978-10-27| CS205116B2|1981-04-30| DD137238A5|1979-08-22| ATA187578A|1985-12-15| DE2813558C2|1983-01-05| FR2385763B1|1980-12-05| AT380962B|1986-08-11| US4229273A|1980-10-21| HU180453B|1983-03-28| NL7803234A|1978-10-03| BR7801971A|1978-12-26| DE2813558A1|1978-10-12| BE865071A|1978-07-17| GB1598754A|1981-09-23|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 RU2555704C2|2009-09-15|2015-07-10|Новартис Аг|Prepolymers, applicable for manufacturing contact lenses, absorbing ultraviolet radiation| RU2576622C2|2010-07-30|2016-03-10|Новартис Аг|Amphiphilic polysiloxane prepolymers and their application|FR1526934A|1966-12-01|1968-05-31|Commissariat Energie Atomique|Process for preparing hydrophilic silicones by radiochemical grafting| US3959102A|1973-08-06|1976-05-25|Essilor International |Method for preparing a crosslinked graft copolymer of silicone and polyvinylpyrrolidone for use as a contact lens, and a contact lens produced thereby| GB1480880A|1974-05-06|1977-07-27|Bausch & Lomb|Shaped body of a simultaneously interpenetrating network polymer and method of preparing same|DE3004685C2|1980-02-08|1986-07-31|Titmus Eurocon Kontaktlinsen GmbH, 8750 Aschaffenburg|Process for making contact lenses made of silicone rubber hydrophilic| EP0220919A3|1985-10-21|1989-04-12|Shin-Etsu Chemical Co., Ltd.|Contact lens| US4983702A|1988-09-28|1991-01-08|Ciba-Geigy Corporation|Crosslinked siloxane-urethane polymer contact lens| US4968532A|1989-01-13|1990-11-06|Ciba-Geigy Corporation|Process for graft copolymerization on surfaces of preformed substrates to modify surface properties| US4978481A|1989-01-13|1990-12-18|Ciba-Geigy Corporation|Process for the encapsulation of preformed substrates by graft copolymerization| US5274028A|1990-12-06|1993-12-28|Baxter International Inc.|Polyvinyl pyrrolidone-grafted coatings on preformed polymers| US7468398B2|1994-09-06|2008-12-23|Ciba Vision Corporation|Extended wear ophthalmic lens| US5760100B1|1994-09-06|2000-11-14|Ciba Vision Corp|Extended wear ophthalmic lens| EP0814116A1|1996-06-19|1997-12-29|Hüls Aktiengesellschaft|Hydrophilic coating of polymeric substrate surfaces| US6132561A|1997-10-13|2000-10-17|Mincher; Bruce J.|Process for the solvent extraction for the radiolysis and dehalogenation of halogenated organic compounds in soils, sludges, sediments and slurries| AU6014301A|2000-03-24|2001-10-03|Novartis Ag|Novel polymers| DE60223668T2|2001-04-27|2008-10-30|Eyesense Ag|KIT FOR MEASURING BLOOD SUGAR CONCENTRATIONS| US7438411B2|2005-05-07|2008-10-21|Nanospectra Biosciences, Inc.|Plasmon resonant based eye protection| CA2671740C|2006-12-13|2015-08-11|Novartis Ag|Actinically curable silicone hydrogel copolymers and uses thereof| MX2009010116A|2007-03-22|2009-10-12|Novartis Ag|Prepolymers with dangling polysiloxane-containing polymer chains.| BRPI0809151A2|2007-03-22|2014-09-16|Novartis Ag|PREPOLYMERS CONTAINING SILICON WITH PENDING HYDROPHILIC POLYMER CHAINS| US8044111B2|2007-11-30|2011-10-25|Novartis Ag|Actinically-crosslinkable silicone-containing block copolymers| US8506856B2|2007-12-10|2013-08-13|Novartis Ag|Method for making silicone hydrogel contact lenses|
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申请号 | 申请日 | 专利标题 FR7709766A|FR2385763B1|1977-03-31|1977-03-31| 相关专利
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